Bismuth based oxide superconductor thin films and method of manufacturing the same

ABSTRACT

A Bi-based oxide superconductor thin film whose c-axis is oriented parallel to the substrate and whose a-axis (or b-axis) is oriented perpendicular to the substrate, is manufactured in order to obtain a high performance layered Josephson junction using a Bi-based oxide superconductor. The method of manufacturing an a-axis oriented Bi-based oxide superconductor thin film, involves an epitaxial growth process using an LaSrAlO 4  single crystal substrate of a (110) plane or a LaSrGaO 4  single crystal substrate of a (110) plane, for which the lattice constant matches well with a (100) plane of a Bi-2223 oxide superconductor. By this method, rather than the normally easily obtained Bi-2212, an a-axis oriented film of Bi-2223 showing an extremely high superconductive transition temperature even for a Bi-based oxide superconductor can be selectively manufactured.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 11/228,787, filed Sep. 16, 2005, in which benefit of and priority tois claimed to Japanese Patent Application No. 2004-273999, filed Sep.21, 2004, and Japanese Patent Application No. 2005-090130, filed in Mar.25, 2005, which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to an oxide superconductor with a c-axisoriented parallel to a substrate and an a-axis (or b-axis) orientedperpendicular to the substrate, especially to bismuth based (hereunder“Bi-based”) oxide superconductor thin films, specificallyBi₂Sr₂Ca₂Cu₃O_(10±X) (where X is a positive number less than unity,hereunder “Bi-2223”) or Bi₂Sr₂CuO_(6±Y) (where Y is a positive numberless than unity, hereunder “Bi-2201”), in order to obtain a highperformance layered Josephson junction using an oxide superconductorespecially a Bi-based oxide superconductor, and a method ofmanufacturing the same.

DESCRIPTION OF RELATED ART

A feature of a Josephson device, which uses a superconductor, is itshigh speed operation and low power consumption. When applied to anintegrated circuit, it can perform high speed switching with littleelectric power. In addition to the high speed switching, the Josephsondevice shows a small heat production than a high density integratedcircuit, in which heat production is a problem common to semiconductordevices. Therefore, it is expected that the Josephson device exhibits ahigher speed operation performance compared to a semiconductor.

Conventionally, Nb metal or NbN was used as a superconductor in aJosephson device. However, because the superconductive transitiontemperature is low, the Josephson device was usually operated at aliquid helium temperature of 4.2K. Compared to this, since an oxidesuperconductor has a higher superconductive transition temperature, aJosephson device using an oxide superconductor can be operated at arounda liquid nitrogen temperature, and thus be it is favorable in the viewof resource and energy saving.

A superconductive device that shows the Josephson effect is called aJosephson junction. A Josephson junction, which is suitable forconstituting an integrated circuit using superconductive devices, isfavorable to be manufactured as a layered junction that has a very thinbarrier layer of a normal conductor or an insulator inserted between twosuperconductive thin films as shown in FIG. 1, as it enables precisedimensional control and the manufacture of many junctions. In practice,a laminated junction is also being used as a Josephson junction insuperconductive integrated circuits using Nb metal.

A problem that requires a breakthrough in order to realize manufacturingof a layered Josephson junction using an oxide superconductor, isclosely related to the crystal structure of oxide superconductors.Yttrium based (hereunder “Y-based”) oxide superconductors and Bi-basedoxide superconductors have more remarkable anisotropy of superconductivecharacteristics such as coherence length, magnetic flux penetrationdepth, or critical current density, than for conventionalsuperconductors such as Nb.

The crystals of these superconductors have orthorhombic lattice ortetragonal lattice structure, but the strength of the superconductivecoupling in the c-axis direction is weaker than the coupling in thein-plane direction of a surface that is perpendicular to the c-axis.Superconductivity of an oxide superconductor is thought to occur in aCuO plane composed of a copper (Cu) atom and an oxygen (O) atom.

Therefore, the anisotropy of the superconductive coupling derives fromthe fact that the CuO plane is oriented perpendicular to a c-axis(namely, in the a- or b-axis direction), and not in the c-axisdirection. Accordingly, the coherence length (the inter-electronicdistance in which a superconducting electron pair is formed) which isclosely related in a Josephson junction, is significantly shorter in thec-axis direction than in the a-axis direction. This tendency is moreremarkable in a Bi-based superconductor, whose crystal structure hasbigger anisotropy than that of a Y-based superconductor, and thecoherence length in the c-axis direction is as short as 0.2 nm.

Thus, an oxide superconductor, especially a Bi-based superconductor suchas Bi-2223 or Bi-2201 has extremely short coherence length in the c-axisdirection. Therefore, in order to manufacture a Josephson junctionlayered in the c-axis direction using c-axis oriented films it isessential to form a flat and very thin barrier layer. However, in makinga barrier layer very thin, a rough surface caused by deposit and so onbecomes a problem, which makes it difficult to form a very thin uniformbarrier layer, and which causes current leakage between superconductorssandwiching the barrier layer from each side. Therefore this type ofJosephson junction has not been obtained yet. Moreover, even if theJosephson junction can be formed, the Josephson critical current densityJc and the Josephson characteristic parameter IcRn are small, and goodcharacteristics may not be obtained.

Accordingly, in order to obtain a high performance layered Josephsonjunction using a Bi-based oxide superconductor, it is essential tomanufacture a junction in the non c-axis direction in which thecoherence length is longer than in the c-axis direction. Among thesedirections, the direction in which the coherence length is the longestis the a-axis (or b-axis) direction. Therefore, in order to obtain ahigh performance layered Josephson junction using a Bi-based oxidesuperconductor, it is preferable to manufacture a Bi-based oxidesuperconductor thin film whose c-axis is oriented parallel to thesubstrate and whose a-axis (or b-axis) is oriented perpendicular to thesubstrate.

As one of the methods to realize this, there is known (JapaneseUnexamined Patent Application, First Publication No. Hei 5-7027) amethod of manufacturing an oxide superconductor film comprising; a stepfor forming a composition modulated film composed of oxides on asubstrate by supplying active oxygen and a part of the metalliccomponents of a Bi-based oxide onto the substrate, and a step forforming an oxide superconductor thin film on the composition modulatedfilm by supplying active oxygen and all of the metallic components ofthe Bi-based oxide. However, according to this method, the proportion ofthe c-axis that is parallel to the substrate varies depending onconditions, and it can not be said that a Bi-based oxide superconductorthin film of good quality can be obtained.

Another method is proposed (Japanese Unexamined Patent Application,First Publication No. Hei 9-246611) that a Josephson device using aBi-based oxide superconductor thin film whose c-axis is orientedparallel to the substrate and whose a-axis (or b-axis) is orientedperpendicular to the substrate, has excellent performance. However,there is no disclosure of any specific process to obtain the goodquality Bi-based oxide superconductor thin film whose c-axis is orientedparallel to the substrate and whose a-axis (or b-axis) is orientedperpendicular to the substrate.

SUMMARY OF THE INVENTION

Consequently, it is an object of the present invention to manufacture awell-crystallized and a-axis (or b-axis) oriented Bi-based oxidesuperconductor thin film, in order to obtain a high performance layeredJosephson junction using a Bi-based oxide superconductor.

In a Bi-2223 thin film, an a-axis oriented Bi-2223 thin film is grown bya process where one unit cell of Bi-2223 is conformity with three unitsof either; a single crystal substrate of LaSrAlO₄ having a (110) plane,a single crystal substrate of LaSrGaO₄ having a (110) plane, a singlecrystal substrate of α-Al₂O₃ having a (10-10) plane (a-plane), or asingle crystal substrate of NdAlO₃ having a (10-10) plane (a-plane).

In a Bi-2201 thin film, an a-axis oriented Bi-2201 thin film is grown bya process where one unit cell of Bi-2201 is matched with two units ofeither; a single crystal substrate of either LaSrAlO₄ having a (110)plane, a single crystal substrate of LaSrGaO₄ having a (110) plane, asingle crystal substrate of α-Al₂O₃ having a (10-10) plane (a-plane), ora single crystal substrate of NdAlO₃ having a (10-10) plane (a-plane).

Normally, when forming a film directly on a substrate at hightemperature, a c-axis oriented Bi-2223 thin film or Bi-2201 thin filmgrows. However when forming a film at substrate temperatures between 500and 600° C., a c-axis oriented film cannot be formed, and awell-crystallized a-axis oriented Bi-2223 or Bi-2201 thin film can bemanufactured.

When manufacturing a Josephson device using a well-crystallized a-axisoriented Bi-based oxide superconductor thin film made by the method ofthe present application, it is possible to obtain a Josephson device ofextremely high performance.

A method of manufacturing a Bi-based oxide superconductive film, whichcomprises the steps of depositing a Bi₂Sr₂Ca₂Cu₃O₁₀ (Bi-2223) oxide filmby carrying out epitaxial growth of Bi₂Sr₂Ca₂Cu₂O₁₀ on a (110) crystalplane of a single crystal substrate of LaSrAlO₄ or on a (110) crystalplane of a single crystal substrate of LasrGaO₄, and crystal axis of theoxide film in which c-axis of the Bia₂Sr₂Ca₂Cu₃O₁₀ oxide is oriented inparallel to the said substrate and a- or b-axis is oriented inperpendicular to the substrate surface.

The Bi-based oxide superconductive film has been obtained by epitaxialgrowth of Bi₂Sr₂Ca₂Cu₃O_(10±X) (Bi-2223) on a (110) crystal plane of asingle crystal substrate of LaSrAlO₄ or on a (110) crystal plane of asingle crystal substrate of LaSrGaO₄, for controlling orientation of thecrystal planes such that c-axis of the Bi₂Sr₂Ca₂Cu₃O_(10±X) (Bi-2223)oxide film is oriented parallel to the said substrate and a- or b-axisis oriented perpendicular to the substrate surface.

Furthermore, a Josephson device has been manufactured using aBi₂Sr₂Ca₂Cu₃O_(10±X) oxide superconductor thin film formed according tothe above-described method exhibits superior performance.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a promising example of a Josephson junction.

FIG. 2 is an explanatory drawing of a matching state.

FIG. 3 is a conceptual drawing of an MOCVD thin film forming device.

FIG. 4 shows a thin film X-ray diffraction patterns for epitaxiallygrown Bi-2223 film and LaSrAlO₄ substrate.

FIG. 5 shows temperature dependence of resistivity of an a-axis orientedBi-2223 thin film.

FIG. 6 shows an interatomic force microscope (AFM) image of a Bi-2223thin film surface.

FIG. 7 is schematic drawing for explaining surface morphology.

DETAILED DESCRIPTION OF THE INVENTION

The most preferred embodiment according to the present invention will bedescribed hereunder.

FIG. 2 shows conformity of lattice constants of a (110) plane of asingle crystal substrate of LaSrAlO₄ and lattice constants of a-axisoriented Bi-2223 formed thereon. As shown in FIG. 2, it is understoodthat one unit cell of Bi-2223 is in conformity with three unit cells ofLaSrAlO₄ extremely well. It is also understood that the misfit of thelattice constants for the a-axis length (or b-axis length) and thec-axis length are −1.48% and 1.61%, respectively, which is extremelysmall.

Therefore, on a (110) LaSrAlO₄ single crystal substrate, a Bi-2223 thinfilm whose c-axis is oriented parallel to the substrate and whose a-axis(or b-axis) is oriented perpendicular to the substrate, can be formed bya heteroepitaxial growth process.

Moreover, it is clear from the conformity that, not a twin crystal film,but a high quality single crystal of Bi-2223 film with the c-axis of theBi-2223 oriented in one direction on the substrate can be manufactured.

Example 1

Using (110) crystal plane of LaSrAlO₄ single crystal substrate, awell-crystallized a-axis oriented Bi-2223 superconductor thin film wasmanufactured by metal-organic chemical vapor deposition (MOCVD). TheMOCVD device is shown in FIG. 3. The film was formed under the followingconditions; Bi(C₆H₅)₃, Sr(DPM)₂, Ca(DPM)₂, and Cu(DPM)₂ (DPM:dipivaloylmethan) were used as metal-organic materials while eachtemperature was maintained at 72° C., 176° C., 161° C., and 80° C.,respectively; the Ar carrier gas flow rate was 100, 300, 300, 70 sccm,respectively; the total pressure was 50 torr; the oxygen partialpressure was 23 torr; and the substrate temperature was 570° C.

The obtained X-ray diffraction pattern is shown FIG. 4. As it is clearfrom the figure, all of the diffraction peaks except for the substratecan be identified as the (n00) or (0n0) plane of the Bi-2223. Accordingto this, it is confirmed that a Bi-2223 thin film whose c-axis isoriented parallel to the substrate and whose a-axis (or b-axis) isoriented perpendicular to the substrate was manufactured.

FIG. 5 shows the temperature dependence of the resistivity of themanufactured a-axis oriented Bi-2223 thin film. Measurement wasperformed by the standard four terminal method.

FIG. 6 shows an interatomic force microscope (AFM) image of the thinfilm surface. Bi-2223, according to its crystal structure, is expectedto grow slowly in the c-axis direction and fast in the a- and b-axisdirections (namely the c-plane), and if the growth proceeds by a twodimensional nucleus growth mechanism, it is expected to have a surfacemorphology as shown in the schematic drawing of FIG. 7.

The surface morphology of a practically obtained a-axis (or b-axis)oriented film proves this, and thus it is understood that the film wasformed by a two dimensional nucleus growth mechanism. Moreover, it isunderstood that a high quality film was obtained without having a twincrystal and whose c-axis is grown uniformly along one direction.

As described above, by carrying out an epitaxial growth on a (110)crystal plane of LaSrAlO₄ single crystal substrate, lattice constants ofwhich are well in conformity with a (100) or (010) plane of a Bi-2223oxide superconductor, the Bi-2223 thin film whose c-axis is oriented andaligned in a parallel direction of the substrate, and whose a-axis (orb-axis) is oriented perpendicular to the substrate, was successfullymanufactured for the first time in the world. In addition to the (110)crystal plane of the LaSrO₄ single crystal substrate, a (110) crystalplane of a LaSrGa₄ single crystal can be used for the substrate ofepitaxial growth deposition for the oxide superconductor film.

Moreover, for this method, if the aforementioned substrate is used, filmforming methods other than the MOCVD method, such as a sputteringmethod, a pulse laser deposition method (PLD method), or a reactivedeposition method are also effective.

While preferred embodiments of the invention have been described andillustrated above, it should be understood that these are exemplary ofthe invention and are not to be considered as limiting. Additions,omissions, substitutions, and other modifications can be made withoutdeparting from the spirit or scope of the present invention.Accordingly, the invention is not to be considered as being limited bythe foregoing description, and is only limited by the scope of theappended claims.

1. A method of manufacturing an oxide superconductor thin film on asubstrate, wherein a lattice constant of a single crystal of saidsuperconductor thin film is approximately integer times multiple of alattice constant of a single crystal of said substrate.
 2. A method ofmanufacturing an oxide superconductor thin film according to claim 1,wherein said oxide superconductor thin film is a Bi₂Sr₂Ca₂Cu₃O_(10±X)(where X is a positive number less than unity) or a Bi₂Sr₂CuO_(6±Y)(where Y is a positive number less than unity) thin film.
 3. A method ofmanufacturing an oxide superconductor thin film according to claim 1,wherein said single crystal substrate is selected from the groupconsisting α-Al₂O₃ and NdAlO₃.
 4. A method of manufacturing an oxidesuperconductor thin film according to claim 2, wherein said singlecrystal substrate is selected from the group consisting α-Al₂O₃ andNdAlO₃.
 5. An oxide superconductor thin film deposited on a substrate,wherein a lattice constant of a single crystal of said thin film is anapproximate integer multiple of a lattice constant of a single crystalof said substrate.
 6. An oxide superconductor thin film according toclaim 5, wherein said oxide superconductor thin film is represented byBi₂Sr₂Ca₂Cu₃O_(10±X) (where X is a positive number less than unity) orBi₂Sr₂CuO_(6±Y) (where Y is a positive number less than unity).
 7. Anoxide superconductor thin film according to claim 5, wherein saidsuperconductor thin film is deposited on a single crystal substrateselected from the group consisting of α-Al₂O₃ and NdAlO₃.
 8. An oxidesuperconductor thin film according to claim 6, wherein saidsuperconductor thin film is deposited on a single crystal substrateselected from the group consisting of α-Al₂O₃ and NdAlO₃.
 9. A Josephsondevice manufactured using an oxide superconductor thin film according toclaim
 5. 10. A Josephson device manufactured using an oxidesuperconductor thin film according to claim
 6. 11. A Josephson devicemanufactured using an oxide superconductor thin film according to claim7.
 12. A Josephson device manufactured using an oxide superconductorthin film according to claim
 8. 13. A method of manufacturing aBia₂Sr₂Ca₂Cu₃O_(10±X) (where X is a positive number less than unity)oxide superconductive film, wherein the Bi₂Sr₂Ca₂Cu₃O_(10±X)superconductor oxide film is manufactured by carrying out epitaxialgrowth of Bi₂Sr₂Ca₂Cu₃O_(10±X) on a (10-10) crystal plane of a singlecrystal substrate of a α-Al₂O₃ or on a (10-10) crystal plane of a singlecrystal substrate of NdAlO₃ such that a c-axis of the Bi₂Sr₂Ca₂Cu₃O₁₀oxide is oriented parallel to the said substrate and an a-axis or b-axisis oriented perpendicular to the substrate surface.
 14. ABi₂Sr₂Ca₂Cu₃O_(10±X) (where X is a positive number less than unity)oxide superconductive film, obtained by epitaxial growth ofBi₂Sr₂Ca₂Cu₂O_(10±X) on a (10-10) crystal plane of a single crystalsubstrate of α-Al₂O₃ or on a (10-10) crystal plane of a single crystalof NdAlO₃ such that a c-axis of the Bia₂Sr₂Ca₂Cu₃O_(10±X) oxide film isoriented parallel to the said substrate and an a-axis or b-axis isoriented perpendicular to the substrate surface.
 15. A Josephson devicemanufactured using a Bia₂Sr₂Ca₂Cu₃O_(10±X) oxide superconductor thinfilm according to claim 14.